阅读说明：本技术 一种稀土/ClO2复合材料及其制备方法 (Rare earth/ClO2Composite material and preparation method thereof ) 是由 郝素娥 张荡 庄志强 孔超宁 王晴 郝璐瑜 何欢 马占鑫 于 2021-01-30 设计创作，主要内容包括：一种稀土/ClO-2复合材料及其制备方法,属于消杀材料研究技术领域。本发明的目的是为了解决目前二氧化氯的吸附和释放问题,所述复合材料包括固体材料、ClO-2溶液和稀土元素,所述ClO-2溶液的浓度为3000～6000ppm。所述方法为：将亚氯酸钠与柠檬酸混合后,加水,并定容；将固体材料加入到上述ClO-2溶液中,再加入0.1mol/L的稀土溶液,浸渍3-5小时,产物经抽滤,并于70～100℃下干燥处理1～3h即可。本发明通过稀土、无机消毒剂、多孔材料的复合,发挥了稀土与ClO-2无机抗菌消毒剂以及多孔吸附材料的协同作用,达到了对各种细菌、病毒等微生物和SO-2、苯、甲醛等化学污染物的高效同时祛除,实现了高效杀毒、灭菌、净化效果。(Rare earth/ClO 2 A composite material and a preparation method thereof belong to the technical field of research of disinfection materials. The invention aims to solve the problem of the adsorption and release of chlorine dioxide at present, and the composite material comprises a solid material and ClO 2 Solution and rare earth element, said ClO 2 The concentration of the solution is 3000-6000 ppm. The method comprises the following steps: will be provided withMixing sodium chlorite and citric acid, adding water and fixing the volume; adding solid material to ClO 2 And adding 0.1mol/L rare earth solution into the solution, dipping for 3-5 hours, carrying out suction filtration on the product, and drying at 70-100 ℃ for 1-3 hours. The invention exerts the effects of rare earth and ClO by compounding rare earth, inorganic disinfectant and porous material 2 The synergistic effect of the inorganic antibacterial disinfectant and the porous adsorption material achieves the aim of treating various bacteria, viruses and other microorganisms and SO 2 And chemical pollutants such as benzene, formaldehyde and the like are efficiently and simultaneously removed, and the effects of high-efficiency disinfection, sterilization and purification are realized.)

1. Rare earth/ClO₂A composite material characterized by: the composite material comprises a solid material and ClO₂Solution and rare earth element, said ClO₂The concentration of the solution is 3000-6000 ppm.

2. A rare earth/ClO as claimed in claim 1₂A composite material characterized by: the solid material is one of a high polymer material, an inorganic porous material or an agricultural and sideline waste resource material.

3. A rare earth/ClO as claimed in claim 2₂A composite material characterized by: the high polymer material is EVA or TPE; the inorganic porous material is one of modified medical stone, modified zeolite or molecular sieve; the agricultural and sideline waste resource material is peanut shells or orange peels.

4. A rare earth/ClO as claimed in claim 1₂A composite material characterized by: the ClO₂The solution is prepared by reacting sodium chlorite, citric acid and water according to a certain proportion.

5. A rare earth/ClO as claimed in claim 1₂A composite material characterized by: the rare earth elements comprise one or more of La, Pr, Nd, Sm, Er, Ce, Eu, Dy, Gd or Ho.

6. A method as claimed in claim 1Rare earth/ClO₂A composite material characterized by: the composite material also comprises water-soluble essence, and the volume fraction of the water-soluble essence is controlled to be 3-5%.

7. A rare earth/ClO as claimed in claim 6₂A composite material characterized by: the water-soluble essence is one of rose essence, jasmine essence, mint essence, sandalwood essence, pineapple essence or lemon essence.

8. A rare earth/ClO as defined in any one of claims 1 to 7₂The preparation method of the composite material is characterized by comprising the following steps: the method specifically comprises the following steps:

the method comprises the following steps: ClO₂The preparation process of the solution comprises the following steps: mixing sodium chlorite and citric acid, adding water and fixing the volume; the ratio of the sodium chlorite to the citric acid to the volume after constant volume is 1g to 0.8 g: 100 mL;

step two: the preparation process of the composite material comprises the following steps: adding solid material to ClO₂Adding 0.1mol/L rare earth solution into the solution, dipping for 3-5 hours, carrying out suction filtration on the product, and drying at 70-100 ℃ for 1-3 hours; the ClO₂The volume ratio of the solution to the rare earth solution is 100: 0.1 to 0.5.

9. A rare earth/ClO as claimed in claim 8₂The preparation method of the composite material is characterized by comprising the following steps: in the second step, when the solid material is EVA or TPE, every 100ml of ClO₂Adding 50-60g of the solution; when the solid material is modified medical stone, modified zeolite or molecular sieve, every 100ml of ClO₂Adding 60-70g of the solution; when the solid material is peanut shell or orange peel, every 100ml of ClO₂10-20g of the solution is added.

Technical Field

The invention belongs to the technical field of research on sterilizing materials, and particularly relates to rare earth/ClO₂Composite materials and methods for making the same.

Background

The traditional chemical disinfectants which are widely applied at present comprise ten types of chlorine-containing disinfectants, guanidine disinfectants, iodine-containing disinfectants, quaternary ammonium salt disinfectants, bromine-containing disinfectants, glutaraldehyde disinfectants, ethanol disinfectants, phenol disinfectants, peroxide disinfectants and chlorine dioxide disinfectants. The main products currently used for epidemic prevention, control and disinfection are as follows: alcohol, 84 disinfectant, chlorine dioxide and the like, and has the problems of flammability, explosiveness, unsafe use, poor concentration control, harm to human bodies due to high concentration, poor sterilization and disinfection effects and the like. Wherein, ClO₂The disinfectant has good performance, is a green disinfectant internationally recognized at present, and is widely applied to the fields of disinfection, deodorization, air purification and the like. Chlorine dioxide (ClO)₂) The microbial cell wall has strong adsorption and penetration capacity, can effectively oxidize enzymes containing sulfydryl in cells, quickly inhibit the synthesis of microbial protein to destroy microbes, and efficiently inactivate various viruses, bacteria and propagules; can also remove inorganic substances such as reduced iron, manganese, sulfide and the like in water by oxidation andcontains organic matters such as aldehyde group, double bond and the like, does not generate chlorination reaction with the organic matters, does not generate halogenated disinfection byproducts with three-effect, and is widely applied to the fields of drinking water treatment, food preservation, paper pulp bleaching, aquaculture, hospital disinfection, public environment space disinfection and the like. Researches show that the chlorine dioxide has good bactericidal effects on viruses, bacteria, fungi and spores, such as hepatitis A and B virus, herpes virus, poliovirus, tubercle bacillus, escherichia coli, typhoid bacillus, staphylococcus aureus, bacteriophage, giardia lamblia cyst, bacterial spores and the like.

Chlorine dioxide has good killing effect on various viruses, and research and application of chlorine dioxide on avian influenza virus sterilization tests show that 80mg/L of chlorine dioxide can kill avian influenza virus by 100%.

However, the chlorine dioxide gas is very active and unstable, is easily dissolved in water and is not easy to store, and the concentration of the chlorine dioxide in the air is more than 10 percent (mass fraction) which has explosion risk but less than 50 mu g/m³There is no obvious sterilization effect, and when ClO is used₂When the use concentration exceeds the normal range, human and animal sensory organs, mucous membranes and nervous systems are affected, so that the function of the human body is damaged, and the application of the composition is limited.

Therefore, studies have been made to use solid porous materials such as molecular sieves, kaolin or high molecular polymers as adsorbents to stabilize the ClO₂The solution and the releasing agent are directly sprayed on the adsorbent, and the adsorption type granular, powdery or flaky immobilized chlorine dioxide is prepared after mixing and molding. However, the existing chlorine dioxide solid preparation has the problems of complex manufacturing process, higher cost, unstable release rate, short action period, poor late-stage effect and the like, wherein the controllable release of the concentration of chlorine dioxide is always a difficult obstacle to overcome, and the requirements of safety, harmlessness, sterilization and disinfection are difficult to meet. Therefore, the problem of how to improve the release stability of the immobilized chlorine dioxide, how to control the release rate and the sterilization characteristic becomes a bottleneck problem which needs to be solved at present.

Disclosure of Invention

The invention aims to solve the problems of adsorption and release of chlorine dioxide at present and provides rare earth/ClO₂Composite materials and methods for making the same.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

rare earth/ClO₂Composite material comprising a solid material, ClO₂Solution and rare earth element, said ClO₂The concentration of the solution is 3000-6000 ppm.

The rare earth/ClO₂The preparation method of the composite material comprises the following specific steps:

the method comprises the following steps: ClO₂The preparation process of the solution comprises the following steps: mixing sodium chlorite and citric acid, adding water and fixing the volume; the ratio of the sodium chlorite to the citric acid to the volume after constant volume is 1g to 0.8 g: 100 mL;

step two: the preparation process of the composite material comprises the following steps: adding solid material to ClO₂Adding 0.1mol/L rare earth solution into the solution, dipping for 3-5 hours, carrying out suction filtration on the product, and drying at 70-100 ℃ for 1-3 hours; the ClO₂The volume ratio of the solution to the rare earth solution is 100: 0.1 to 0.5.

Compared with the prior art, the invention has the beneficial effects that:

the invention adopts materials with strong adsorption capacity, low price, easily obtained raw materials such as EVA (ethylene-vinyl acetate copolymer), medical stone, peanut shell, molecular sieve and the like as the immobilized ClO₂The novel rare earth composite anti-epidemic material is prepared by the unique disinfection and sterilization effect and the catalytic modification effect of the rare earth. The material has rare earth and ClO₂The synergistic disinfection and sterilization effect of the composite material, and simultaneously, the composite material obtained has the advantages of slow release capability, stable release amount, long release period and the like through the action of the rare earth. Meanwhile, essence such as lemon, rose and the like is added into the material, so that the material has pleasant fragrance. The composite material can be processed into materials with various shapes and sizes, is convenient to use, and can be applied to public places such as hospitals, schools, enterprises and hotels; is also easy to carry, and is suitable for the elderly and children in various stages.

The invention provides that the controllable release of the concentration of the dioxide rate of the immobilized product is realized by adding rare earth ions in the process of the immobilization of the dioxide rate. Further research shows that the rare earth element has a certain sterilization effect on bacteria and viruses, so that the rare earth element and the chlorine dioxide disinfectant are effectively compounded, and the sterilization effect and the stability of the product are obviously improved. The composite material obtained by the invention has high adsorption efficiency, good chemical stability and uniform and stable release rate, and has unique advantages in the fields of disinfection and epidemic prevention.

The invention has low cost, high sterilization and disinfection effect, safe and slow-release long-term stability, flexible portability, air pollutant elimination and environment purification, important application value, strong market competitiveness and immeasurable market development requirement.

(1) The multifunctional, wide range of killing: by compounding rare earth, inorganic disinfectant and porous material, the rare earth and ClO are exerted₂The synergistic effect of the inorganic antibacterial disinfectant and the porous adsorption material achieves the aim of treating various bacteria, viruses and other microorganisms and SO₂And chemical pollutants such as benzene, formaldehyde and the like are efficiently and simultaneously removed, and the effects of high-efficiency disinfection, sterilization and purification are realized.

(2) High efficiency: the unique bactericidal and antiviral effects of the rare earth are utilized, and the specific killing effect of the composite material on various bacteria and viruses is obviously improved.

(3) Long-term stability: the ClO of the porous solid material is realized through the action of the rare earth and the slow release function of the porous material₂The high-efficiency adsorption and controllable release of the catalyst improve the pure ClO₂The product release rate is not controllable, the action time is short, and the like, the sterilization effect can be ensured for more than 1 month, and the application in long-time sterilization and disinfection occasions can be met.

(4) Safety: chlorine dioxide is generated by the reaction of sodium chlorite and citric acid, the in-situ absorption is carried out by utilizing porous materials such as medical stone and the like, the effective concentration control and the slow release effect of the disinfectant are realized by the regulation effect of rare earth, and the ClO is ensured₂Is in a safe and effective range for a long time.

(5) Simple and easy portability: the raw materials used are wide in source, low in cost, simple in manufacturing process, free of special equipment, capable of being processed into portable products and easy to carry and use.

Drawings

FIG. 1 is ClO₂The sterilization and disinfection effect comparison chart;

FIG. 2 is a rare earth/ClO₂The sterilization and disinfection effects of the composite material are compared.

Detailed Description

The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

The first embodiment is as follows: the present embodiment describes a rare earth/ClO₂Composite material comprising a solid material, ClO₂Solution and rare earth element, said ClO₂The concentration of the solution is 3000-6000 ppm.

The second embodiment is as follows: detailed description of the preferred embodiment₂The composite material is one of a high polymer material, an inorganic porous material or an agricultural and sideline waste resource material.

The third concrete implementation mode: rare earth/ClO as described in the second embodiment₂The composite material is prepared from EVA or TPE; the inorganic porous material is one of modified medical stone, modified zeolite or molecular sieve; the agricultural and sideline waste resource material is peanut shells or orange peels.

The fourth concrete implementation mode: detailed description of the preferred embodiment₂Composite material of said ClO₂The solution is prepared by reacting sodium chlorite, citric acid and water according to a certain proportion.

The fifth concrete implementation mode: detailed description of the preferred embodiment₂A composite material of the rare earth element includingOne or more of La, Pr, Nd, Sm, Er, Ce, Eu, Dy, Gd or Ho.

The sixth specific implementation mode: detailed description of the preferred embodiment₂The composite material also comprises water-soluble essence, and the volume fraction of the water-soluble essence is controlled to be 3-5%. Not only can increase the fragrance, but also is helpful for sterilization.

The seventh embodiment: sixth embodiment A rare earth/ClO₂The water-soluble essence is one of rose essence, jasmine essence, mint essence, sandalwood essence, pineapple essence or lemon essence.

The specific implementation mode is eight: rare earth/ClO as set forth in any one of embodiments one to seven₂The preparation method of the composite material comprises the following specific steps:

the method comprises the following steps: ClO₂The preparation process of the solution comprises the following steps: mixing sodium chlorite and citric acid, adding water and fixing the volume; the ratio of the sodium chlorite to the citric acid to the volume after constant volume is 1g to 0.8 g: 100 mL;

step two: the preparation process of the composite material comprises the following steps: adding solid material to ClO₂Adding 0.1mol/L rare earth solution into the solution, dipping for 3-5 hours, carrying out suction filtration on the product, and drying at 70-100 ℃ for 1-3 hours; the ClO₂The volume ratio of the solution to the rare earth solution is 100: 0.1 to 0.5.

The specific implementation method nine: detailed description of an embodiment eighth rare earth/ClO₂The preparation method of the composite material comprises the second step, when the solid material is EVA or TPE, every 100ml of ClO₂Adding 50-60g of the solution; when the solid material is modified medical stone, modified zeolite or molecular sieve, every 100ml of ClO₂Adding 60-70g of the solution; when the solid material is peanut shell or orange peel, every 100ml of ClO₂10-20g of the solution is added.

Example 1:

after mixing 10g of sodium chlorite with 8g of citric acid, water was added and the volume was set to 1000 mL. Adding 600g Maifanitum into 1000ml of above ClO₂Adding 0.1mol/L SmCl into the solution₃30ml of the solution was immersed for 5 hours. And carrying out suction filtration on the product, and drying at 100 ℃ for 2 h to obtain the product.

Example 2:

after mixing 5g of sodium chlorite and 4g of citric acid, water was added and the volume was adjusted to 500 mL. 250g of EVA material was added to 500ml of ClO as described above₂To the solution was added 0.1mol/L of CeCl₃25ml of the solution, 15ml of lemon essence is added, and the mixture is soaked for 5 hours. And carrying out suction filtration on the product, and drying at 70 ℃ for 1 h to obtain the product.

Example 3:

after mixing 1.0g of sodium chlorite and 0.8g of citric acid, water was added and the volume was adjusted to 100 mL. Adding 20g peanut shell to 100ml of ClO₂To the solution was added 0.1mol/L ErCl₃2ml of the solution and immersed for 5 hours. And carrying out suction filtration on the product, drying at 80 ℃ for 3h, and further processing and forming to obtain the product.

The application effect of the product is as follows:

（1）ClO₂adsorption and release effects: the results of the study show that the products obtained in the above examples, and the control group (ClO alone)₂Sample), due to the addition of rare earth, the solid materials such as medical stone, EVA, peanut shell and the like are aligned to ClO₂The absorption rate is improved by 1.5-1.8 times, slow and effective release is realized, and the release rate can be maintained at 0.05-0.1 mg/m within 1 month³Within the range.

(2) And (3) sterilization and disinfection effects:

the results of the study showed that the product obtained in the above example, and the control group (ClO alone)₂Sample), a long-term stable sterilization and disinfection effect of the composite material is realized. Through a control experiment for 1 month, the sterilization and disinfection effects of the obtained product and a control group are shown in figures 1 and 2, wherein figure 1 shows the surface fungus growth condition of the prepared agar culture medium after being placed for 5 days, and the growth of various fungi on the culture medium is obviously seen; FIG. 2 shows rare earth/ClO-doped samples obtained in example 1₂The surface fungus growth of the agar medium of the composite material after 1 month of standing (the pictures of examples 2 and 3 are similar to those of example 1, and example 1 is taken as a representative explanation), and it can be seen thatIn the rare earth/ClO₂Under the action of the composite material, after the culture medium is placed for 1 month, no fungus grows, which indicates that the prepared rare earth/ClO₂The composite material has strong sterilization and disinfection effects.

(3) Air disinfection effect: the product is placed in a sterilizing environment to be naturally volatilized, 5g-10g of the product is placed in each cubic meter of space, the sterilizing time is 30 minutes, the sterilizing rate reaches 100%, and the removing rate of air pollutants such as formaldehyde reaches more than 99%.